CN102757067A - Titanium-silicon molecular sieve, preparation method thereof and method for preparing cyclohexanone oxime by using molecular sieve - Google Patents

Titanium-silicon molecular sieve, preparation method thereof and method for preparing cyclohexanone oxime by using molecular sieve Download PDF

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CN102757067A
CN102757067A CN2011104425399A CN201110442539A CN102757067A CN 102757067 A CN102757067 A CN 102757067A CN 2011104425399 A CN2011104425399 A CN 2011104425399A CN 201110442539 A CN201110442539 A CN 201110442539A CN 102757067 A CN102757067 A CN 102757067A
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titanium
molecular sieves
silicon
making
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陈雅萍
谢正发
姚秉铎
江建章
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China Petrochemical Development Corp
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
    • C01B39/085—Group IVB- metallosilicates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
    • C01B39/087—Ferrosilicates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes

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Abstract

A titanium-silicon molecular sieve and its preparation method, said preparation method comprises mixing titanium source, silicon source, transition metal source, template agent and water; heating the mixed compounds to form a colloidal mixture; carrying out a hydrothermal step; and calcining the colloidal mixture subjected to the hydrothermal treatment to obtain the titanium-silicon molecular sieve. The invention also provides a method for preparing cyclohexanone oxime, which takes the titanium-silicon molecular sieve as a catalyst and can achieve the advantages of high conversion rate and selectivity and high hydrogen peroxide utilization rate when being used for preparing cyclohexanone oxime.

Description

Titanium-si molecular sieves and method for making thereof and the method for using this molecular sieve manufacturing OxiKhim-Styrol
Technical field
The present invention relates to a kind of titanium-si molecular sieves and method for making thereof, especially, relate to a kind of titanium-si molecular sieves and method for making thereof with transition metal.
Background technology
Crystallization titanium-silicalite molecular sieve catalyst is that titanium atom is introduced in the reticulated structure of silicon-dioxide; The crystalline form that crystalline form with MFI structure is TS-1 molecular sieve and MEL structure is the TS-2 molecular sieve; Be widely applied is being in the oxidizing reaction of oxygenant with the ydrogen peroxide 50; Wherein, the ME of existing commercialization running has cyclohexanone oxamidinating and phenol hydroxylation.
In industry; OxiKhim-Styrol is to produce indispensable intermediate product in the hexanolactam operation; Utilizing pimelinketone, ammonia and ydrogen peroxide 50 is that method that catalyzer is made OxiKhim-Styrol has disclosed in No. 4968842, No. 5227525, No. 5312987 and No. 6828459 USP with titanium-si molecular sieves; When adopting this method, making simply and not needs through acid hydroxylammonium intermediate product, but all there is a problem in above-mentioned method; The service efficiency that is ydrogen peroxide 50 is confined to 89% to 90%, can't promote ydrogen peroxide 50 efficient again and cause manufacturing cost to improve.
In addition; No. 5290533 USP and No. 226258 European patent have disclosed a kind of HTS compound method that contains transition metal; But its synthesis mode is earlier to produce precipitation of hydroxide after the WITH AMMONIA TREATMENT with source of iron; This throw out is mixed with titanium-silicon mixed solution through washing, neutralization and after being dissolved in the template after filtering again, and heating and moisturizing produce molecular sieve through hydro-thermal then, and this synthesis step is numerous and diverse tediously long.
Therefore, how a kind of simplification molecular sieve synthetic method for making is provided, and the catalyst applications of gained can improve the performance of oximation reaction and promote ydrogen peroxide 50 usefulness when making OxiKhim-Styrol, be problem urgently to be separated in fact.
Therefore, for previous technical disadvantages, the present invention provides an effective solution, simplifies the molecular sieve synthesis flow, and is applied in the manufacturing OxiKhim-Styrol, with performance and the lifting ydrogen peroxide 50 usefulness that improves the cyclohexanone oxamidinating reaction.
Summary of the invention
The shortcoming of prior art in view of the above, the present invention promptly provides a kind of method for making of titanium-si molecular sieves, comprising: the mixture of preparing to have titanium source, silicon source, transition metal source, template and water; Heat said mixture, to form colloid admixture; Said colloid admixture is carried out hydrothermal step; And calcine said colloid admixture through hydrothermal treatment consists, to obtain titanium-si molecular sieves.
In method for making of the present invention, the mol ratio of said template and silicon is for being less than or equal to 0.5.The transition metal source of using is to be selected from metal hydrogen salt, metal alkyl oxide and metal complex.Preferably, said transition metal source is to be dissolved in the water, sneaks into titanium source, silicon source and template to form mixture with the form of the aqueous solution.For example, said transition metal source is to be soluble in the water that contains ammonia.
Again, the method for making of titanium-si molecular sieves of the present invention, also can be included in form colloid admixture after, in said colloid admixture, sneak into water or silicon sol, again the colloid admixture of sneaking into water or silicon sol is carried out hydrothermal step.
Usually, said silicon sol is the silicon dioxide colloid aqueous solution, and said dioxide-containing silica be said silicon sol 0.1 to 50wt%.In addition, the weight ratio scope of said silicon sol and said colloid admixture to be mixed is 0.001 to 0.5: 1.
According to aforesaid method for making, the present invention further provides a kind of titanium-si molecular sieves, comprising: silicon oxide; Titanium oxide; And transition metal oxide, wherein, the titanium of said titanium-si molecular sieves and the mol ratio of silicon are 0.005 to 0.1; The transition metal of said transition metal oxide and the mol ratio of silicon are 0.00001 to 0.05.
In another embodiment; The present invention also provides a kind of method of making OxiKhim-Styrol; Comprise: utilize titanium-si molecular sieves of the present invention as catalyzer, under the condition that solvent exists, make the reactant that comprises pimelinketone, ammonia, ydrogen peroxide 50 react the formation OxiKhim-Styrol.
By on can know that the method for making of titanium-si molecular sieves of the present invention is before forming colloid admixture; Promptly earlier transition metal source is sneaked in titanium source, silicon source and the template; Make the titanium-si molecular sieves of gained have transition metal oxide, as catalyzer, be used in when making OxiKhim-Styrol with said titanium-si molecular sieves; Can reach high conversion and selection rate, and the advantage of high ydrogen peroxide 50 rate of utilization.
Description of drawings
Fig. 1 is the catalyzer X-Ray collection of illustrative plates of embodiment 2.
Embodiment
Below, through specific specific examples embodiment of the present invention being described, those skilled in the art can understand advantage of the present invention and effect easily by the content that this specification sheets disclosed.The present invention also can other different mode implement, and, not being contrary under the prerequisite of disclosed technological thought, can give different modifications and change that is.
The present invention provides a kind of method for making of titanium-si molecular sieves, comprising: the mixture of preparing to have titanium source, silicon source, transition metal source, template and water; Heat said mixture, to form colloid admixture; Said colloid admixture is carried out hydrothermal step; And calcine said colloid admixture through hydrothermal treatment consists, to obtain titanium-si molecular sieves.
Usually, be with the silicon source with after template is mixed, add the titanium source and the transition metal source aqueous solution more in regular turn.Employed titanium source is a tetraalkyl titanate, for example tetraethyl-titanic acid ester, tetra isopropyl titanate or tetra-n-butyl titanic acid ester.Tetraalkyl silicon ester or polyethoxye silane then can be used in the silicon source, for example, and tetramethylsilane acid esters, tetraethyl silicane acid esters, tetrapropyl-sisicane acid esters and tetrabutyl silicane acid esters; Polyethoxye silane such as ES-28 (n=1～2), ES-32 (n=3～4) and ES-40 (n=4～5) (manufacturer is Colcoat Co., Ltd.).The titanium source that the present invention uses and the kind in silicon source are not limited to above-mentioned each person, and can be selected from a kind of or make up the multiple method of the present invention of carrying out.
Employed template is the aqueous solution or the alcoholic solution of n-propyl volatile caustic among the present invention; For example, template can be dissolved in the aqueous solution or alcoholic solution by four n-propyl bromination ammoniums, makes through anion-exchange resin; Wherein, Alcoholic solution can be the alcohols with 1 to 5 carbon atom, for example, is selected from one or more solvents in the group that is made up of methyl alcohol, ethanol, Virahol, propyl carbinol and the trimethyl carbinol.In addition, the template concentration that is dissolved in the solvent can be 5wt% to 50wt%, and preferred concentration is 20wt% to 40wt%.Again, the mol ratio of said template and silicon is for being less than or equal to 0.5.
Above-mentioned transition metal source is to be selected from metal hydrogen salt, metal alkyl oxide and metal complex, and sneaks into titanium source, silicon source, reaches in the template with the form of the aqueous solution.The element of transition metal source of the present invention is to be selected from one or more of periodictable IB to VIIIB, is preferably vanadium, iron, cobalt, nickel, zinc, yttrium, zirconium, ruthenium, palladium and hafnium.
In the mixture of the titanium source of method for making of the present invention, silicon source, transition metal source, template and water, the molar ratio range of titanium and silicon is 0.005 to 0.1, and preferable range is 0.015 to 0.08, and most preferred range is 0.02 to 0.05; The molar ratio range of transition metal source and silicon is 0.00001 to 0.05, and preferable range is 0.0003 to 0.03, and most preferred range is 0.0005 to 0.02; The mol ratio of water and silicon is 10 to 80, and preferable range is 20 to 60, and most preferred range is 30 to 50; The mol ratio of template and silicon is 0.1 to 0.5, and preferable range is 0.15 to 0.45, and most preferred range is 0.2 to 0.4.
In addition, method for making of the present invention is sneaked into water or silicon sol after also can being included in and forming colloid admixture in said colloid admixture, again the colloid admixture of sneaking into water or silicon sol is carried out hydrothermal step.Usually, be to mix with the form of the silicon dioxide colloid aqueous solution, and said dioxide-containing silica be said silicon sol 0.1 to 50wt%.The dioxide/silica gel liquid solution; Like Du Pont Ludox AS-40, Ludox AS-30, Ludox AM-30, Ludox TM-40, Ludox TM-50, Ludox AM-30, Ludox HS-30 and Ludox HS-40 or the daily output chemistry SNOWTEX-40 that provides, SNOWTEX-50, SNOWTEX-C, SNOWTEX-N, SNOWTEX-20L, SNOWTEX-ZL, SNOWTEX-UP or its combination are provided, and are not limited thereto.Moreover the weight ratio scope of said silicon sol and said colloid admixture to be mixed is 0.001 to 0.5: 1.
According to aforesaid method for making, titanium-si molecular sieves of the present invention is to comprise: silicon oxide; Titanium oxide; And transition metal oxide, wherein, the titanium of said titanium-si molecular sieves and the mol ratio of silicon are 0.005 to 0.1; The transition metal of said transition metal oxide and the mol ratio of silicon are 0.00001 to 0.05.The transition metal atoms of said transition metal oxide is to be positioned at outside the skeleton or skeleton of said molecular sieve.
The present invention also provides a kind of method of making OxiKhim-Styrol, comprising: utilize titanium-si molecular sieves of the present invention as catalyzer, under the condition that solvent exists; At 40 ℃ to 110 ℃; Be preferably under 50 ℃ to 90 ℃ the temperature of reaction and 1 atmospheric reaction pressure, make the reactant that comprises pimelinketone, ammonia, ydrogen peroxide 50 react the formation OxiKhim-Styrol, wherein; The mol ratio of said ammonia and pimelinketone is 1.2: 1 to 2: 1, and preferable range is 1.4 to 1.8.The mol ratio of said ydrogen peroxide 50 and pimelinketone is 0.7: 1 to 2.0: 1, and preferable range is 1.0 to 1.5.Solvent can be polar solvent, one or more solvents in the cohort of forming like alcohol, ketone and water, with the trimethyl carbinol for most preferably; And the usage quantity of said catalyzer is to account for 0.1 to 10% with the total restatement of said reactant, is preferably 1 to 5%.
In addition, hydrogen peroxide concentration can be 30wt% to 70wt%, and the ydrogen peroxide 50 feed mode is to add reactive system with the reaction times stepped start-stop system.
Comparative example 1
This instance is to prepare the titanium-si molecular sieves that does not add transition metal source, with as comparative example.
500 milliliters of round-bottomed flasks are carried out the nitrogen envelope in vacuum system; Get 1.98 gram tetra-n-butyl titanic acid ester and add round-bottomed flask; Temperature is cooled to 5 ℃, then the anhydrous isopropyl alcohol of 20 grams is added and begin simultaneously to stir, treat that getting 30 gram tetraethyl silicane acid esters after the temperature equilibrium dropwise adds; Stir and get 56 gram (20wt%) four n-propyl ammonium hydroxide aqueous solutions after 1 hour and dropwise add in the above-mentioned solution, alcohol is removed in the back that stirs under 85 ℃ to add water to gross weight again be that 100g can accomplish colloid admixture.This colloid admixture is enclosed in hydro-thermal jar, and 180 ℃ of hydro-thermals 120 hours, after solid and liquid separation, solid part to neutral, 100 ℃ of dryings and 550 ℃ of calcinings 8 hours, got final product the output catalyzer with washing.
Embodiment 1 to 13 is that the HTS of the various MOXs of explanation is synthetic
Embodiment 1
V-TS-1 prepares (catalyst A)
500 milliliters of round-bottomed flasks are carried out the nitrogen envelope in vacuum system; Get 1.932 gram tetra-n-butyl titanic acid ester adding nitrogen envelope round-bottomed flasks and temperature and be cooled to 5 ℃; Treating to get after the temperature equilibrium 30.27 gram tetraethyl silicane acid esters dropwise adds; Stir get after 1 hour 56.5 the gram (content 20wt%) four n-propyl volatile caustic aqueous isopropanols dropwise add; The hydration vanadylic sulfate of getting 0.19g after the completion is dissolved in 20 milliliters the water, and this vanadium source aqueous solution is dropwise added, and alcohol is removed in the back that stirs under 85 ℃ to add water to gross weight again be that 100g can accomplish colloid admixture.This colloid admixture is enclosed in hydro-thermal jar, and in 180 ℃ of hydro-thermals 120 hours, after solid and liquid separation, solid part to neutral, in 100 ℃ of dryings and 550 ℃ of calcinings 8 hours, got final product the output catalyzer with washing.
Embodiment 2
Fe-TS-1 prepares (catalyst B)
500 milliliters of round-bottomed flasks are carried out the nitrogen envelope in vacuum system; Get 1.98 gram tetra-n-butyl titanic acid ester adding nitrogen envelope round-bottomed flasks and temperature and be cooled to 5 ℃; Treating to get after the temperature equilibrium 30 gram tetraethyl silicane acid esters dropwise adds; Stir get after 1 hour 56 the gram (content 20wt%) four n-propyl volatile caustic aqueous isopropanols dropwise add; The ferric chloride (FeCl36H2O) of getting 0.39g after the completion is dissolved in 20 milliliters the water, and this source of iron aqueous solution is dropwise added, and the back that stirs adds water to gross weight again after removing alcohol under 85 ℃ be that 100g can accomplish colloid admixture.This colloid admixture is enclosed in hydro-thermal jar, and 180 ℃ of hydro-thermals 120 hours, after solid and liquid separation, solid part to neutral, 100 ℃ of dryings and 550 ℃ of calcinings 8 hours, got final product the output catalyzer with washing, and its X-Ray collection of illustrative plates is as shown in Figure 1.The prepared catalyzer of the embodiment of the invention all has the MFI structure through detecting.
Embodiment 3
Co-TS-1 prepares (catalyzer C)
500 milliliters of round-bottomed flasks are carried out the nitrogen envelope in vacuum system; Get 1.98 gram tetra-n-butyl titanic acid ester adding nitrogen envelope round-bottomed flasks and temperature and be cooled to 5 ℃; Treating to get after the temperature equilibrium 30 gram tetraethyl silicane acid esters dropwise adds; Stir get after 1 hour 56 the gram (content 20wt%) four n-propyl volatile caustic aqueous isopropanols dropwise add; The Cobalt diacetate tetrahydrate of getting 0.0143g after the completion is dissolved in 20 milliliters the water, and this cobalt source aqueous solution is dropwise added, and the back that stirs adds water to gross weight again after removing alcohol under 85 ℃ be that 100g can accomplish colloid admixture.This colloid admixture is enclosed in hydro-thermal jar, and 180 ℃ of hydro-thermals 120 hours, after solid and liquid separation, solid part to neutral, 100 ℃ of dryings and 550 ℃ of calcinings 8 hours, got final product the output catalyzer with washing.
Embodiment 4
Ni-TS-1 prepares (catalyzer D)
500 milliliters of round-bottomed flasks are carried out the nitrogen envelope in vacuum system; Get 1.99 gram tetra-n-butyl titanic acid ester adding nitrogen envelope round-bottomed flasks and temperature and be cooled to 5 ℃; Treating to get after the temperature equilibrium 30.6 gram tetraethyl silicane acid esters dropwise adds; Stir get after 1 hour 57 the gram (content 20wt%) four n-propyl volatile caustic aqueous isopropanols dropwise add; The six water nickelous chlorides of getting 0.0012g after the completion are dissolved in 20 milliliters the water, and this nickel source aqueous solution is dropwise added, and the back that stirs adds water to gross weight again after removing alcohol under 85 ℃ be that 100g can accomplish colloid admixture.This colloid admixture is enclosed in hydro-thermal jar, and 180 ℃ of hydro-thermals 120 hours, after solid and liquid separation, solid part to neutral, 100 ℃ of dryings and 550 ℃ of calcinings 8 hours, got final product the output catalyzer with washing.
Embodiment 5
Zn-TS-1 prepares (catalyzer E)
500 milliliters of round-bottomed flasks are carried out the nitrogen envelope in vacuum system; Get 1.98 gram tetra-n-butyl titanic acid ester adding nitrogen envelope round-bottomed flasks and temperature and be cooled to 5 ℃; Treating to get after the temperature equilibrium 30 gram tetraethyl silicane acid esters dropwise adds; Stir get after 1 hour 56 the gram (content 20wt%) four n-propyl volatile caustic aqueous isopropanols dropwise add; The zinc nitrate hexahydrate of getting 0.17g after the completion is dissolved in 20 milliliters the water, and this zinc source aqueous solution is dropwise added, and the back that stirs adds water to gross weight again after removing alcohol under 85 ℃ be that 100g can accomplish colloid admixture.This colloid admixture is enclosed in hydro-thermal jar, and 180 ℃ of hydro-thermals 120 hours, after solid and liquid separation, solid part to neutral, 100 ℃ of dryings and 550 ℃ of calcinings 8 hours, got final product the output catalyzer with washing.
Embodiment 6
Zr-TS-1 prepares (catalyzer F)
500 milliliters of round-bottomed flasks are carried out the nitrogen envelope in vacuum system; Get 1.98 gram tetra-n-butyl titanic acid ester adding nitrogen envelope round-bottomed flasks and temperature and be cooled to 5 ℃; Treating to get after the temperature equilibrium 30.54 gram tetraethyl silicane acid esters dropwise adds; Stir get after 1 hour 57 the gram (content 20wt%) four n-propyl volatile caustic aqueous isopropanols dropwise add; The tetrahydrated zirconium sulfate of getting 0.024g after the completion is dissolved in 20 milliliters the water, and this zirconium source aqueous solution is dropwise added, and the back that stirs adds water to gross weight again after removing alcohol under 85 ℃ be that 100g can accomplish colloid admixture.This colloid admixture is enclosed in hydro-thermal jar, and 180 ℃ of hydro-thermals 120 hours, after solid and liquid separation, solid part to neutral, 100 ℃ of dryings and 550 ℃ of calcinings 8 hours, got final product the output catalyzer with washing.
Embodiment 7
Ru-TS-1 prepares (catalyzer G)
500 milliliters of round-bottomed flasks are carried out the nitrogen envelope in vacuum system; Get 1.98 gram tetra-n-butyl titanic acid ester adding nitrogen envelope round-bottomed flasks and temperature and be cooled to 5 ℃; Treating to get after the temperature equilibrium 30.14 gram tetraethyl silicane acid esters dropwise adds; Stir get after 1 hour 56 the gram (content 20wt%) four n-propyl volatile caustic aqueous isopropanols dropwise add; The hydration ruthenium chloride of getting 0.016g after the completion is dissolved in 20 milliliters the water, and this ruthenium source aqueous solution is dropwise added, and the back that stirs adds water to gross weight again after removing alcohol under 85 ℃ be that 100g can accomplish colloid admixture.This colloid admixture is enclosed in hydro-thermal jar, and 180 ℃ of hydro-thermals 120 hours, after solid and liquid separation, solid part to neutral, 100 ℃ of dryings and 550 ℃ of calcinings 8 hours, got final product the output catalyzer with washing.
Embodiment 8
Pd-TS-1 prepares (catalyzer H)
500 milliliters of round-bottomed flasks are carried out the nitrogen envelope in vacuum system; Get 1.94 gram tetra-n-butyl titanic acid ester adding nitrogen envelope round-bottomed flasks and temperature and be cooled to 5 ℃; Treating to get after the temperature equilibrium 30.34 gram tetraethyl silicane acid esters dropwise adds; Stir and get 56 gram (content 20wt%) four n-propyl volatile caustic aqueous isopropanols after 1 hour and dropwise add, the Palladous chloride of getting 0.102g after the completion is dissolved in 20 milliliters the ammoniacal liquor, and this palladium source solution is dropwise added; Restir is 1 hour after accomplishing, and the back that stirs adds water to gross weight again after removing alcohol under 85 ℃ be that 100g can accomplish colloid admixture.This colloid admixture is enclosed in hydro-thermal jar, and 180 ℃ of hydro-thermals 120 hours, after solid and liquid separation, solid part to neutral, 100 ℃ of dryings and 550 ℃ of calcinings 8 hours, got final product the output catalyzer with washing.
Embodiment 9
Y-TS-1 prepares (catalyst I)
500 milliliters of round-bottomed flasks are carried out the nitrogen envelope in vacuum system; Get 1.98 gram tetra-n-butyl titanic acid ester adding nitrogen envelope round-bottomed flasks and temperature and be cooled to 5 ℃; Treating to get after the temperature equilibrium 30.05 gram tetraethyl silicane acid esters dropwise adds; Stir get after 1 hour 56 the gram (content 20wt%) four n-propyl volatile caustic aqueous isopropanols dropwise add; The four water acetic acid yttriums of getting 0.153g after the completion are dissolved in 20 milliliters the water, and this yttrium source aqueous solution is dropwise added, and the back that stirs adds water to gross weight again after removing alcohol under 85 ℃ be that 100g can accomplish colloid admixture.This colloid admixture is enclosed in hydro-thermal jar, and 180 ℃ of hydro-thermals 120 hours, after solid and liquid separation, solid part to neutral, 100 ℃ of dryings and 550 ℃ of calcinings 8 hours, got final product the output catalyzer with washing.
Embodiment 10
Hf-TS-1 prepares (catalyzer J)
500 milliliters of round-bottomed flasks are carried out the nitrogen envelope in vacuum system; Get 1.97 gram tetra-n-butyl titanic acid ester adding nitrogen envelope round-bottomed flasks and temperature and be cooled to 5 ℃; Treating to get after the temperature equilibrium 30.13 gram tetraethyl silicane acid esters dropwise adds; Stir get after 1 hour 56 the gram (content 20wt%) four n-propyl volatile caustic aqueous isopropanols dropwise add; The hafnium sulfate of getting 0.154g after the completion is dissolved in 20 milliliters the water, and this hafnium source aqueous solution is dropwise added, and the back that stirs adds water to gross weight again after removing alcohol under 85 ℃ be that 100g can accomplish colloid admixture.This colloid admixture is enclosed in hydro-thermal jar, and 180 ℃ of hydro-thermals 120 hours, after solid and liquid separation, solid part to neutral, 100 ℃ of dryings and 550 ℃ of calcinings 8 hours, got final product the output catalyzer with washing.
Embodiment 11
Cr-TS-1 prepares (catalyzer K)
500 milliliters of round-bottomed flasks are carried out the nitrogen envelope in vacuum system; Get 1.97 gram tetra-n-butyl titanic acid ester adding nitrogen envelope round-bottomed flasks and temperature and be cooled to 5 ℃; Treating to get after the temperature equilibrium 30.11 gram tetraethyl silicane acid esters dropwise adds; Stir get after 1 hour 56 the gram (content 20wt%) four n-propyl volatile caustic aqueous isopropanols dropwise add; The nine water chromium nitrates of getting 0.002g after the completion are dissolved in 20 milliliters the water, and this chromium source aqueous solution is dropwise added, and the back that stirs adds water to gross weight again after removing alcohol under 85 ℃ be that 100g can accomplish colloid admixture.This colloid admixture is enclosed in hydro-thermal jar, and 180 ℃ of hydro-thermals 120 hours, after solid and liquid separation, solid part to neutral, 100 ℃ of dryings and 550 ℃ of calcinings 8 hours, got final product the output catalyzer with washing.
Embodiment 12
Mn-TS-1 prepares (catalyzer L)
500 milliliters of round-bottomed flasks are carried out the nitrogen envelope in vacuum system; Get 1.98 gram tetra-n-butyl titanic acid ester adding nitrogen envelope round-bottomed flasks and temperature and be cooled to 5 ℃; Treating to get after the temperature equilibrium 30.4 gram tetraethyl silicane acid esters dropwise adds; Stir get after 1 hour 57 the gram (content 20wt%) four n-propyl volatile caustic aqueous isopropanols dropwise add; The manganous sulfate of getting 0.001g after the completion is dissolved in 20 milliliters the water, and this manganese source aqueous solution is dropwise added, and the back that stirs adds water to gross weight again after removing alcohol under 85 ℃ be that 100g can accomplish colloid admixture.This colloid admixture is enclosed in hydro-thermal jar, and 180 ℃ of hydro-thermals 120 hours, after solid and liquid separation, solid part to neutral, 100 ℃ of dryings and 550 ℃ of calcinings 8 hours, got final product the output catalyzer with washing.
Embodiment 13
Add the Fe-TS-1 preparation (catalyzer M) of silicon sol
500 milliliters of round-bottomed flasks are carried out the nitrogen envelope in vacuum system; Get 1.98 gram tetra-n-butyl titanic acid ester adding nitrogen envelope round-bottomed flasks and temperature and be cooled to 5 ℃; Treating to get after the temperature equilibrium 30 gram tetraethyl silicane acid esters dropwise adds; Stir get after 1 hour 56 the gram (content 20wt%) four n-propyl volatile caustic aqueous isopropanols dropwise add; The ferric chloride (FeCl36H2O) of getting 0.23g after the completion is dissolved in 20 milliliters the water, and this source of iron aqueous solution is dropwise added, and the back that stirs after removing alcohol under 85 ℃, adds 10.80g Ludox AS-40 again and water to gross weight is that 100g can accomplish mixing solutions.This mixing solutions is enclosed in hydro-thermal jar, and 180 ℃ of hydro-thermals 120 hours, after solid and liquid separation, solid part to neutral, 100 ℃ of dryings and 500 ℃ of calcinings 8 hours, got final product the output catalyzer with washing.
Embodiment 14
Present embodiment carries out the cyclohexanone oxamidinating reaction test with comparative example 1 and 1 to 8 synthetic catalyzer of embodiment, and embodiment is following:
Get the 0.55g catalyzer and place three-necked bottle; Adding 5g pimelinketone, the 28.5g trimethyl carbinol and 4.7g and concentration again is the ammoniacal liquor of 28wt%; Loading onto prolong and stirring system, after the question response temperature rises to 60 ℃, is the aqueous hydrogen peroxide solution (ketone: H of 35wt% with 4.96g and concentration 2O 2=1.0: 1.0) adding reactive system with 5 hour reaction times, after the ydrogen peroxide 50 charging is accomplished 1 hour, carry out catalyzer and separate with reaction solution, the reaction test result of analytical reaction liquid is as shown in table 1.
Table 1
Figure BSA00000645163800101
X a=pimelinketone transformation efficiency=pimelinketone consumes mole number/pimelinketone and drops into mole number * 100%
S b=OxiKhim-Styrol selection rate=OxiKhim-Styrol output mole number/pimelinketone consumes mole number * 100%
X c=ydrogen peroxide 50 transformation efficiency=ydrogen peroxide 50 consumes mole number/ydrogen peroxide 50 and drops into mole number * 100%
S d=ydrogen peroxide 50 selection rate=OxiKhim-Styrol output mole number/ydrogen peroxide 50 consumes mole number * 100%
Embodiment 15
Present embodiment carries out the cyclohexanone oxamidinating reaction test with comparative example 1, embodiment 2 and 9 to 12 synthetic catalyzer of embodiment, and embodiment is following:
Get the 0.55g catalyzer and place three-necked bottle; Adding 5g pimelinketone, the 28.5g trimethyl carbinol and 4.7g and concentration is the ammoniacal liquor of 28wt%; Loading onto prolong and stirring system, after the question response temperature rises to 60 ℃, is the aqueous hydrogen peroxide solution (ketone: H of 35wt% with 5.20g and concentration 2O 2=1.00: 1.05) adding reactive system with 5 hour reaction times, after the ydrogen peroxide 50 charging is accomplished 1 hour, carry out catalyzer and separate with reaction solution, reaction solution is analyzed, reaction test result such as table 2.
Table 2
Figure BSA00000645163800111
Embodiment 16
Present embodiment carries out the cyclohexanone oxamidinating reaction test with comparative example 1, embodiment 1,2,3,5 and 13 synthetic catalyzer, and embodiment is following:
Get the 0.55g catalyzer and place three-necked bottle; Adding 5g pimelinketone, the 28.5g trimethyl carbinol and 4.7g and concentration is the ammoniacal liquor of 28wt%; Loading onto prolong and stirring system, after the question response temperature rises to 60 ℃, is the aqueous hydrogen peroxide solution (ketone: H of 35wt% with 5.35g and concentration 2O 2=1.00: 1.08) adding reactive system with 5 hour reaction times, after the ydrogen peroxide 50 charging is accomplished 1 hour, carry out catalyzer and separate with reaction solution, reaction solution is analyzed, reaction test result such as table 3.
Table 3
Figure BSA00000645163800121
In sum, the method for making of titanium-si molecular sieves of the present invention is before forming colloid admixture; Promptly earlier transition metal source is sneaked in titanium source, silicon source and the template; Make the titanium-si molecular sieves of gained have transition metal oxide, as catalyzer, be used in when making OxiKhim-Styrol with said titanium-si molecular sieves; Can reach high conversion and selection rate, and the advantage of high ydrogen peroxide 50 rate of utilization.
Above-mentioned specification sheets and embodiment are merely illustrative principle of the present invention and effect thereof, but not are used to limit the present invention.Rights protection scope of the present invention should be listed like claims.

Claims (22)

1. the method for making of a titanium-si molecular sieves comprises:
Preparation has the mixture of titanium source, silicon source, transition metal source, template and water;
Heat said mixture, to form colloid admixture;
Said colloid admixture is carried out hydrothermal step; And
Calcine said colloid admixture, to obtain titanium-si molecular sieves through hydrothermal treatment consists.
2. the method for making of titanium-si molecular sieves as claimed in claim 1 is characterized in that, said titanium source is a tetraalkyl titanate.
3. the method for making of titanium-si molecular sieves as claimed in claim 1 is characterized in that, said silicon source is tetraalkyl silicon ester or polyethoxye silane.
4. the method for making of titanium-si molecular sieves as claimed in claim 1 is characterized in that, said template is a TPAOH.
5. the method for making of titanium-si molecular sieves as claimed in claim 1; It is characterized in that said template is dissolved in the solvent, make the concentration of said template reach 5wt% to 50wt%; And said solvent is an alcoholic solvent, and the step of said heated mixt is to be used to remove said solvent.
6. the method for making of titanium-si molecular sieves as claimed in claim 5 is characterized in that, said alcoholic solvent is one or more solvents that are selected from the group that is made up of methyl alcohol, ethanol, Virahol, propyl carbinol and the trimethyl carbinol.
7. the method for making of titanium-si molecular sieves as claimed in claim 1 is characterized in that, the mol ratio of said template and silicon is for being less than or equal to 0.5.
8. the method for making of titanium-si molecular sieves as claimed in claim 1 is characterized in that, said transition metal source is to be selected from metal hydrogen salt, metal alkyl oxide and metal complex.
9. the method for making of titanium-si molecular sieves as claimed in claim 8 is characterized in that, said transition metal source is to be dissolved in the water, sneaks into titanium source, silicon source and template to form mixture with the form of the aqueous solution.
10. the method for making of titanium-si molecular sieves as claimed in claim 1 is characterized in that, said transition metal source is to be dissolved in the water that contains ammonia.
11. the method for making of titanium-si molecular sieves as claimed in claim 1 is characterized in that, the titanium of said titanium-si molecular sieves and the mol ratio of silicon are 0.005 to 0.1; The mol ratio of said transition metal and silicon is 0.00001 to 0.05.
12. the method for making of titanium-si molecular sieves as claimed in claim 1 is characterized in that, also be included in form colloid admixture after, in said colloid admixture, sneak into water or silicon sol, again the colloid admixture of sneaking into water or silicon sol is carried out hydrothermal step.
13. the method for making of titanium-si molecular sieves as claimed in claim 12 is characterized in that, said silicon sol is the silicon dioxide colloid aqueous solution, and said dioxide-containing silica be said silicon sol 0.1 to 50wt%.
14. the method for making of titanium-si molecular sieves as claimed in claim 12 is characterized in that, the weight ratio scope of said silicon sol and said colloid admixture to be mixed is 0.001 to 0.5: 1.
15. a titanium-si molecular sieves comprises:
Silicon oxide;
Titanium oxide; And
Transition metal oxide,
The titanium of said titanium-si molecular sieves and the mol ratio of silicon are 0.005 to 0.1; The transition metal of said transition metal oxide and the mol ratio of silicon are 0.00001 to 0.05.
16. titanium-si molecular sieves as claimed in claim 15 is characterized in that, the transition metal atoms of said transition metal oxide is to be positioned at outside the skeleton or skeleton of said molecular sieve.
17. a method of making OxiKhim-Styrol comprises:
Utilize the described titanium-si molecular sieves of claim 15 as catalyzer, under the condition that solvent exists, make the reactant that comprises pimelinketone, ammonia, ydrogen peroxide 50 react the formation OxiKhim-Styrol.
18. the method for manufacturing OxiKhim-Styrol as claimed in claim 17 is characterized in that, the mol ratio of said ammonia and pimelinketone is 1.2: 1 to 2: 1.
19. the method for manufacturing OxiKhim-Styrol as claimed in claim 17 is characterized in that, the mol ratio of said ydrogen peroxide 50 and pimelinketone is 0.7: 1 to 2.0: 1.
20. the method for manufacturing OxiKhim-Styrol as claimed in claim 17 is characterized in that, said polar solvent is one or more solvents that are selected from the cohort of being made up of alcohol, ketone and water.
21. the method for manufacturing OxiKhim-Styrol as claimed in claim 20 is characterized in that, said solvent is the trimethyl carbinol.
22. the method for manufacturing OxiKhim-Styrol as claimed in claim 17 is characterized in that, the usage quantity of said catalyzer is to account for 0.1 to 10% with the total restatement of said reactant.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104028255A (en) * 2014-05-12 2014-09-10 谷屿 Magnetic surface-modified nanometer titanium dioxide and preparation method thereof
CN106517236A (en) * 2015-09-15 2017-03-22 中国石油化工股份有限公司 Preparation method of titanium silicalite molecular sieve
CN107840344A (en) * 2016-09-21 2018-03-27 中国石油化工股份有限公司 A kind of HTS and its preparation method and application
CN115872896A (en) * 2022-12-05 2023-03-31 衢州巨化锦纶有限责任公司 Preparation method for producing butanone oxime by using nickel-doped titanium silicalite molecular sieve

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI480100B (en) * 2011-04-27 2015-04-11 China Petrochemical Dev Corp Taipei Taiwan Titanium-silicon molecular sieve and its preparation method and method for producing cyclohexanone oxime using the molecular sieve
SG10201407071SA (en) * 2013-10-29 2015-05-28 China Petroleum & Chemical A Full-Si Molecular Sieve and its Synthesis Process
CN105085314B (en) * 2015-08-14 2017-07-28 中国石油化工股份有限公司青岛安全工程研究院 The continuous producing method of cyclohexanone oxime
WO2018088436A1 (en) * 2016-11-11 2018-05-17 Ube Industries, Ltd. Ammoxmation catalyst and process for producing oxime
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CN115999645A (en) * 2023-01-06 2023-04-25 江苏科技大学 Pickering emulsifier and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0272496A1 (en) * 1986-12-23 1988-06-29 ENIRICERCHE S.p.A. Process for oligomerizing light olefines
CN1346705A (en) * 2001-09-13 2002-05-01 大连理工大学 Process for preparing composite catalyst and its application
CN1375455A (en) * 2001-12-28 2002-10-23 大连理工大学 Prepn. of small-grain Ti-Si molecular sieve in cheap hydrothermal system and its application
CN1432560A (en) * 2002-01-10 2003-07-30 中国石油化工股份有限公司 Cyclohexanone oxamidinating process

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1127311B (en) * 1979-12-21 1986-05-21 Anic Spa SYNTHETIC, CRYSTALLINE, POROUS MATERIAL CONSTITUTED BY SILICON AND TITANIUM OXIDES, METHOD FOR ITS PREPARATION AND ITS USES
JPH06644B2 (en) * 1983-09-19 1994-01-05 工業技術院長 Method for producing iron-titanium-metal-containing crystalline silicate
US5290533A (en) 1985-12-19 1994-03-01 Eniricerche S.P.A. Method for production of a coated substrate with controlled surface characteristics
IT1207520B (en) * 1985-12-19 1989-05-25 Eniricerche S P A Snamprogetti SYNTHETIC MATERIAL POROUS CRYSTALLINE CONTAINING SILICON OXIDES TITANIUM AND IRON.
US4794198A (en) * 1986-11-14 1988-12-27 Montedipe S.P.A. Catalytic process for the manufacture of oximes
IT1217899B (en) 1988-06-23 1990-03-30 Montedipe Spa CATALYTIC PROCESS FOR OXYME PRODUCTION
IT1244680B (en) 1991-01-23 1994-08-08 Montedipe Srl MULTI-STAGE PROCESS FOR THE LIQUID STAGE OF CARBONYL COMPOUNDS
IT1255745B (en) 1992-04-01 1995-11-15 Enichem Anic Srl TWO-STAGE PROCESS FOR LIQUID PRODUCTION OF OXIME
JP3509427B2 (en) * 1996-10-07 2004-03-22 株式会社ノリタケカンパニーリミテド Method for producing zeolite membrane
JP4804616B2 (en) * 1999-09-20 2011-11-02 株式会社豊田中央研究所 Porous body and method for producing the same
IT1314263B1 (en) * 1999-12-03 2002-12-06 Enichem Spa PROCESS FOR THE PREPARATION OF ZEOLITHIC CATALYSTS.
TWI324990B (en) 2002-06-28 2010-05-21 Sumitomo Chemical Co Method for producing cyclohexanone oxime
US20040054199A1 (en) * 2002-09-17 2004-03-18 Basf Aktiengesellschaft Process for epoxidation and catalyst to be used therein
JP4262644B2 (en) * 2004-07-16 2009-05-13 ユーオーピー エルエルシー Synthesis method of molecular sieve
JP4635644B2 (en) * 2005-02-28 2011-02-23 住友化学株式会社 Method for producing cyclohexanone oxime
US7528269B2 (en) * 2005-12-20 2009-05-05 Lyondell Chemical Technology, L.P. Process for oxidizing organic compounds
CN101274765B (en) * 2007-03-30 2011-11-30 中国石油化工股份有限公司 Noble metal-contained micropore titanium-silicon material and preparation thereof
ITMI20072342A1 (en) * 2007-12-14 2009-06-15 Polimeri Europa Spa PROCESS TO PREPARE ZEOLITIS TS-1
TWI480100B (en) * 2011-04-27 2015-04-11 China Petrochemical Dev Corp Taipei Taiwan Titanium-silicon molecular sieve and its preparation method and method for producing cyclohexanone oxime using the molecular sieve

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0272496A1 (en) * 1986-12-23 1988-06-29 ENIRICERCHE S.p.A. Process for oligomerizing light olefines
CN1346705A (en) * 2001-09-13 2002-05-01 大连理工大学 Process for preparing composite catalyst and its application
CN1375455A (en) * 2001-12-28 2002-10-23 大连理工大学 Prepn. of small-grain Ti-Si molecular sieve in cheap hydrothermal system and its application
CN1432560A (en) * 2002-01-10 2003-07-30 中国石油化工股份有限公司 Cyclohexanone oxamidinating process

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GABRIEL OVEJERO ET AL.: "Wet Peroxide Oxidation of Phenolic Solutions over Different Iron-Containing Zeolitic Materials", 《INDUSTRIAL AND ENGINEERING CHEMISTRY RESEARCH》 *
L. V. PIRUTKO ET AL.: "Preparation and catalytic study of metal modified TS-1 in the oxidation of benzene to phenol by N2O", 《MICROPOROUS AND MESOPOROUS MATERIALS》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104028255A (en) * 2014-05-12 2014-09-10 谷屿 Magnetic surface-modified nanometer titanium dioxide and preparation method thereof
CN104028255B (en) * 2014-05-12 2015-05-13 谷屿 Magnetic surface-modified nanometer titanium dioxide and preparation method thereof
CN106517236A (en) * 2015-09-15 2017-03-22 中国石油化工股份有限公司 Preparation method of titanium silicalite molecular sieve
CN107840344A (en) * 2016-09-21 2018-03-27 中国石油化工股份有限公司 A kind of HTS and its preparation method and application
CN107840344B (en) * 2016-09-21 2020-08-18 中国石油化工股份有限公司 Titanium-silicon molecular sieve and preparation method and application thereof
CN115872896A (en) * 2022-12-05 2023-03-31 衢州巨化锦纶有限责任公司 Preparation method for producing butanone oxime by using nickel-doped titanium silicalite molecular sieve

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